CN116786145A - Diesel hydrodesulfurization catalyst and preparation method thereof - Google Patents
Diesel hydrodesulfurization catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title abstract description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 37
- 238000007654 immersion Methods 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- 238000005470 impregnation Methods 0.000 claims abstract description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 150000003751 zinc Chemical class 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 7
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001868 cobalt Chemical class 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical group O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 68
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004246 zinc acetate Substances 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical group [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 35
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 118
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 30
- 239000011787 zinc oxide Substances 0.000 description 15
- 239000002283 diesel fuel Substances 0.000 description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 12
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 12
- 238000009835 boiling Methods 0.000 description 11
- 238000005984 hydrogenation reaction Methods 0.000 description 10
- 229910052725 zinc Inorganic materials 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 5
- 229910052596 spinel Inorganic materials 0.000 description 5
- 239000011029 spinel Substances 0.000 description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 2
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- -1 zinc aluminate Chemical class 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- JODIJOMWCAXJJX-UHFFFAOYSA-N [O-2].[Al+3].[O-2].[Zn+2] Chemical compound [O-2].[Al+3].[O-2].[Zn+2] JODIJOMWCAXJJX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a diesel hydrodesulfurization catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: sequentially adding phosphoric acid, molybdenum oxide and nickel or cobalt salt into deionized water, heating, and cooling after the solution is clear and transparent; adding zinc salt and stirring, and fixing the volume after the zinc salt is completely dissolved to obtain metal impregnation liquid; and (3) immersing the carrier in the metal immersion liquid by adopting an isovolumetric immersion method, and drying and roasting to obtain the diesel hydrodesulfurization catalyst. The preparation method can adjust the acting force between the carrier and the active metal, is beneficial to the rapid impregnation of the carrier, and evenly distributes the impregnating solution of the active component in the catalyst carrier, thereby preparing the high-activity diesel hydrodesulfurization catalyst.
Description
Technical Field
The invention relates to a catalyst preparation method in the field of hydrogenation catalysts, in particular to a diesel hydrodesulfurization catalyst which uses VIB and VIII metal as active components.
Background
One of the main tasks of clean diesel oil production is to effectively remove sulfide in diesel oil, the quality standard of the diesel oil is increasingly strict along with the continuous enhancement of environmental protection awareness in recent years, the sulfide content in the diesel oil is strictly limited, and the clean diesel oil with the sulfur content of less than 10 mug/g is currently implemented in the main countries of the world. With the heavy and poor quality of crude oil, sulfur content of various diesel oil fractions in refineries is continuously increased, and the proportion of complex sulfide with larger steric hindrance in the diesel oil fraction is increased, so that the desulfurization difficulty of the diesel oil fraction is increased. Aiming at the diesel oil raw materials with poor properties, the ultra-deep desulfurization of the inferior diesel oil is realized mainly by reducing the processing load of a device, improving the reaction temperature and lowering the final distillation point of the diesel oil at present due to the limitation of the hydrogenation activity of the catalyst, so that the development of a diesel oil hydrodesulfurization catalyst with high activity is required.
The diesel hydrodesulfurization catalyst is mainly a supported catalyst, the carrier is alumina or siliceous alumina, and the catalyst is prepared by impregnating the carrier with an impregnating solution containing active metal by an impregnation method. When the catalyst is prepared by adopting an impregnation method, the property of the active metal impregnation liquid has important influence on the structure, the dispersion condition and the acting force between the active metal impregnation liquid and a carrier of the catalyst, thereby influencing the activity of the catalyst. At present, ni-Mo of VIB and VIII families is generally adopted for the diesel hydrodesulfurization catalystOr Co-Mo bimetal as active component and ammonia water or phosphoric acid as assistant. In order to promote the active metal to form a high-activity hydrogenation active phase, substances such as organic acid, polyalcohol, organic amine and the like are added in the preparation process of the impregnating solution to carry out complexation with the active metal, so that acting force between the carrier and the active metal is regulated, and the active metal is promoted to form the high-activity hydrogenation active phase in the catalyst vulcanization process. Zinc oxide or zinc salt can also be added in the preparation process of the carrier to prepare ZnO-Al 2 O 3 Composite carrier, znO and Al are used 2 O 3 The formed zinc aluminate spinel structure weakens acting force between the carrier and the active component, and is beneficial to the active component to form a high-activity hydrogenation active phase.
Chinese patent CN1325942a discloses a method for preparing a catalyst, which increases the catalyst activity by adding an organic carboxylic acid and a polyol to a metal impregnation liquid. The organic carboxylic acid includes amino triacetic acid, ethylenediamine tetraacetic acid, and citric acid, and the polyalcohol includes mannitol, ethylene glycol, and glycerol. The disadvantages of this technique are: the addition of organic acid or polyol to the metal impregnation liquid increases the viscosity of the impregnation liquid on the one hand, and on the other hand, the impregnation liquid and the catalyst carrier harden due to the relatively high heat release during the impregnation of the alumina carrier, so that the solution is difficult to enter the inside of the carrier, and the distribution of the catalyst active components is uneven.
Chinese patent CN201710158347.2 discloses a catalyst for hydrogenation of raffinate oil, wherein a zinc oxide layered material containing zinc-aluminum spinel is prepared by alternately titrating an aluminum-containing soluble salt solution and a zinc-containing solution at a non-constant pH; uniformly mixing zinc oxide containing zinc aluminate spinel with pseudo-boehmite, adding sesbania powder, an acid solution containing sodium polyacrylate after nitric acid acidification treatment and an aqueous solution of phosphoric acid, potassium nitrate and magnesium nitrate, kneading, molding, drying and roasting to obtain a zinc oxide-aluminum oxide composite carrier; the active component is then supported to prepare the catalyst. The disadvantages of this technique are: the catalyst preparation process is long, and zinc oxide is difficult to uniformly distribute in the carrier.
Disclosure of Invention
The invention aims to develop a diesel hydrodesulfurization catalyst and a preparation method thereof, wherein impregnating solution obtained by the preparation method is uniform and stable, acting force between a carrier and active metal can be regulated, rapid impregnation of the carrier is facilitated, and the impregnating solution is uniformly distributed in the catalyst carrier by active components, so that the high-activity diesel hydrodesulfurization catalyst is prepared.
In order to achieve the above object, the present invention provides a method for preparing a diesel hydrodesulfurization catalyst, comprising:
sequentially adding phosphoric acid, molybdenum oxide and nickel or cobalt salt into deionized water, heating, and cooling after the solution is clear and transparent; adding zinc salt and stirring, and fixing the volume after the zinc salt is completely dissolved to obtain metal impregnation liquid; and (3) immersing the carrier in the metal immersion liquid by adopting an isovolumetric immersion method, and drying and roasting to obtain the diesel hydrodesulfurization catalyst.
The preparation method of the diesel hydrodesulfurization catalyst provided by the invention has the advantages that the heating temperature is 60-100 ℃, and the heating time is 0.5-2 hours.
The preparation method of the diesel hydrodesulfurization catalyst provided by the invention is characterized in that the temperature is reduced to below 40 ℃.
According to the preparation method of the diesel hydrodesulfurization catalyst, molybdenum oxide is preferably molybdenum trioxide, nickel or cobalt salt is preferably basic carbonate, and zinc salt is zinc nitrate or zinc acetate.
The preparation method of the diesel hydrodesulfurization catalyst comprises the step of preparing MoO in a metal impregnating solution by counting metal oxides 3 NiO (or CoO), P 2 O 5 The mass ratio of ZnO is preferably 40-60:7.5-15:4-10:4-8.
The carrier is composed of alumina, and the appearance is clover type. The nature of the support is not particularly limited in the present invention, and the diameter of the support is preferably 1.4 to 1.6mm and the specific surface area is 300 to 400m 2 Per gram, pore volume is 0.5-0.8mL/g.
The drying temperature is preferably 100-140 ℃, and the drying time is preferably 2-5 hours.
The preparation method of the diesel hydrodesulfurization catalyst of the invention has the advantages that the roasting temperature is preferably 400-500 ℃, and the roasting time is preferably 3-6 hours.
The invention also provides a diesel hydrodesulfurization catalyst obtained by the preparation method, wherein the mass of the catalyst is 100%, and the MoO in the catalyst is as follows 3 The content of NiO is preferably 20-28wt%, the content of NiO is preferably 4-6wt%, the content of ZnO is preferably 2-4wt%, and the rest is carrier.
The invention can be further described as follows:
weighing a certain amount of deionized water, adding the deionized water into a beaker, sequentially adding phosphoric acid, molybdenum oxide and nickel or cobalt salts into the deionized water, heating the solution at 60-100 ℃ for 0.5-2 hours, cooling to below 40 ℃ after the solution is clear and transparent, adding zinc salts into the solution, stirring, and adding deionized water into the solution to fix the volume after the zinc salts are completely dissolved. The molybdenum oxide used in the solution preparation process is preferably molybdenum trioxide, the nickel or cobalt salt is preferably basic carbonate, and the zinc salt is zinc nitrate or zinc acetate. MoO in metal impregnation liquid 3 The content is preferably 40-60g/100mL, the content of NiO or CoO is preferably 7.5-15 g/100mL, and the content of P 2 O 5 The content is preferably 4-10g/100mL, and the ZnO content is preferably 4-8g/100mL. The carrier is impregnated by an isovolumetric impregnation method, and the carrier is composed of alumina and has clover-shaped appearance. The nature of the support is not particularly limited in the present invention, and the diameter of the support is preferably 1.4 to 1.6mm and the specific surface area is 300 to 400m 2 And/g, wherein the pore volume is 0.5-0.8mL/g, and the impregnated catalyst wet strip is subjected to health maintenance, drying and roasting to obtain the catalyst. MoO in the catalyst based on 100% of the catalyst mass 3 The content is preferably 20-28wt%, the NiO content is preferably 4-6wt%, the ZnO content is preferably 2-4wt%, and the rest is carrier. The drying temperature of the catalyst is preferably 100-140 ℃, the drying time is preferably 2-5 hours, the roasting temperature of the catalyst is preferably 400-500 ℃, and the roasting time is preferably 3-6 hours.
The invention adopts phosphoric acid as an auxiliary agent, avoids the adverse effect of ammonia water or organic amine on the environment and human body, and prepares uniform and stable Ni-Mo or Co-Mo impregnating solution. In addition, zinc salt is added into the impregnating solution, the alumina carrier is adopted to impregnate the metal impregnating solution in equal volume, and the catalyst is prepared by drying and roasting. In the roasting process of the catalyst, the acting force between the carrier and the active metal nickel or cobalt of the catalyst is regulated by forming competitive adsorption on the alumina carrier by the zinc and the nickel or cobalt in the active metal, so that the active components are promoted to form a high-activity hydrogenation active phase in the subsequent vulcanization process, and the hydrodesulfurization activity of the catalyst is improved. According to the preparation method disclosed by the invention, organic acid or polyalcohol is not used as an auxiliary agent for improving the activity of the catalyst, so that the viscosity of the impregnating solution is reduced, and the uniform distribution of active metals in the catalyst is facilitated. The catalyst has short preparation flow, and zinc is uniformly distributed in the catalyst carrier, so that the acting force between the carrier and the active metal can be regulated.
According to the preparation method disclosed by the invention, the water-soluble salt of zinc is added into the active metal impregnating solution, so that the zinc and the active metal component are jointly supported on the carrier, the zinc and the alumina carrier form a zinc-aluminum spinel structure in the roasting process of the catalyst, the probability of forming inert nickel-aluminum spinel by the active component nickel and alumina is reduced, the utilization efficiency of the active metal is improved, the interaction between the carrier and the active component is regulated, and the active metal is promoted to form a high-activity hydrogenation active phase.
The preparation method of the invention avoids using active improvement auxiliary agents such as organic acid, polyalcohol and the like, reduces the viscosity of the impregnating solution, is beneficial to improving the impregnating effect of the impregnating solution and improves the dispersion uniformity of active metals in the catalyst carrier.
The catalyst has short preparation flow and zinc oxide is uniformly distributed in the catalyst.
Detailed Description
The invention is further illustrated below with reference to examples. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. The experimental procedures in the examples below, without specific details, are generally performed under conditions conventional in the art or recommended by the manufacturer; the raw materials, reagents and the like used, unless otherwise specified, are those commercially available from conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art in light of the above teachings are intended to be within the scope of the invention as claimed.
Raw materials and sources:
the carrier is PHF diesel hydrofining catalyst carrier produced by Shenyang trimerization Kate catalyst Co., ltd, the diameter of the carrier is 1.4-1.6mm, and the specific surface is 300-400m 2 Per gram, pore volume is 0.5-0.8mL/g.
Example 1:
6.5g of phosphoric acid (concentration 85 wt%) and 40.4g of molybdenum trioxide (MoO) were weighed out 3 99wt% of solution, 14.7g of basic nickel carbonate (51 wt% of NiO content) is sequentially added into 100g of deionized water to be heated to boiling, heating is stopped after the solution is clear and transparent, the volume of the solution is fixed to 100mL after the solution is cooled to room temperature, and the solution is marked as 1# solution. Immersing the carrier in the No. 1 solution by an isovolumetric immersion method, observing the immersion effect after the carrier is immersed, drying the immersed carrier at 120 ℃ for 4 hours, and roasting at 450 ℃ for 4 hours to obtain the catalyst, namely the No. 1 catalyst.
Example 2:
9.7g of phosphoric acid (concentration 85 wt%) and 50.5g of molybdenum trioxide (MoO) were weighed out 3 99wt% of solution, 14.7g of basic nickel carbonate (51 wt% of NiO content) is sequentially added into 100g of deionized water to be heated to boiling, heating is stopped after the solution is clear and transparent, the volume of the solution is fixed to 100mL after the solution is cooled to room temperature, and the solution is marked as 2# solution. Immersing the carrier in a No. 2 solution by an isovolumetric immersion method, observing the immersion effect after the carrier is immersed, drying the immersed carrier at 120 ℃ for 4 hours, and roasting at 450 ℃ for 4 hours to obtain the catalyst, namely the No. 2 catalyst.
Example 3:
13.0g of phosphoric acid (concentration 85 wt%) and 58.6g of molybdenum trioxide (MoO) were weighed out 3 99wt% of the solution, 15.7g of basic nickel carbonate (51 wt% of NiO content) is sequentially added into 100g of deionized water to be heated to boiling, heating is stopped after the solution is clear and transparent, the solution is cooled to room temperature and then fixed to 100mL of volume, and the solution is marked as 3# solution. Immersing the carrier in 3# solution by an isovolumetric immersion method, observing the immersion effect after the carrier is immersed, drying the immersed carrier at 120 ℃ for 4 hours, and roasting at 450 ℃ for 4 hours to obtain the catalyst, namely the 3# catalyst.
Example 4:
13.0g of phosphoric acid (concentration 85 wt%) and 58.6g of molybdenum trioxide (MoO) were weighed out 3 99wt% of solution, 19.6g of basic nickel carbonate (51 wt% of NiO content) is sequentially added into 100g of deionized water to be heated to boiling, heating is stopped after the solution is clear and transparent, the solution is cooled to room temperature and then fixed to 100mL of solution, and the solution is marked as No. 4 solution. Immersing the carrier in the No. 4 solution by an isovolumetric immersion method, observing the immersion effect after the carrier is immersed, drying the immersed carrier at 120 ℃ for 4 hours, and roasting at 450 ℃ for 4 hours to obtain the catalyst, namely the No. 4 catalyst.
Example 5:
6.5g of phosphoric acid (concentration 85 wt%) and 40.4g of molybdenum trioxide (MoO) were weighed out 3 99wt percent of content), 14.7g of basic nickel carbonate (51 wt percent of NiO content) are sequentially added into 100g of deionized water to be heated to boiling, heating is stopped after the solution is clear and transparent, 14.8g of zinc nitrate hexahydrate (27 wt percent of ZnO content) is added into the solution after the solution is cooled to room temperature, and the volume of the solution is fixed to 100mL after the solution is completely dissolved, and the solution is marked as a 5# solution. Immersing the carrier in a No. 5 solution by an isovolumetric immersion method, observing the immersion effect after the carrier is immersed, drying the immersed carrier at 120 ℃ for 4 hours, and roasting at 450 ℃ for 4 hours to obtain the catalyst, namely the No. 5 catalyst.
Example 6:
6.5g of phosphoric acid (concentration 85 wt%) and 40.4g of molybdenum trioxide (MoO) were weighed out 3 99wt percent of content), 14.7g of basic nickel carbonate (51 wt percent of NiO content) are sequentially added into 100g of deionized water to be heated to boiling, heating is stopped after the solution is clear and transparent, 29.6g of zinc nitrate hexahydrate (27 wt percent of ZnO content) is added into the solution after the solution is cooled to room temperature, and the volume of the solution is fixed to 100mL after the solution is completely dissolved, and the solution is marked as 6# solution. Immersing the carrier in a 6# solution by an isovolumetric immersion method, observing the immersion effect after the carrier is immersed, drying the immersed carrier at 120 ℃ for 4 hours, and roasting at 450 ℃ for 4 hours to obtain the catalyst, namely the 6# catalyst.
Example 7:
6.5g of phosphoric acid (concentration 85 wt%) and 40.4g of molybdenum trioxide (MoO) were weighed out 3 Content 99 wt%) 14.7g basic Nickel carbonate (NiO content51 wt%) adding 100g deionized water in turn to boil, stopping heating after the solution is clear and transparent, cooling the solution to room temperature, adding 18.2g zinc acetate (ZnO content 44 wt%) into the solution, and after the solution is completely dissolved, fixing volume of the solution to 100mL, and marking as 7# solution. Immersing the carrier in a No. 7 solution by an isovolumetric immersion method, observing the immersion effect after the carrier is immersed, drying the immersed carrier at 120 ℃ for 4 hours, and roasting at 450 ℃ for 4 hours to obtain the catalyst, namely the No. 7 catalyst.
Example 8:
13.0g of phosphoric acid (concentration 85 wt%) and 58.6g of molybdenum trioxide (MoO) were weighed out 3 99wt percent of content), 19.6g of basic nickel carbonate (51 wt percent of NiO content) are sequentially added into 100g of deionized water to be heated to boiling, heating is stopped after the solution is clear and transparent, 14.8g of zinc nitrate hexahydrate (27 wt percent of ZnO content) is added into the solution after the solution is cooled to room temperature, and the volume of the solution is fixed to 100mL after the solution is completely dissolved, and the solution is marked as 8# solution. Immersing the carrier in 8# solution by an isovolumetric immersion method, observing the immersion effect after the carrier is immersed, drying the immersed carrier at 120 ℃ for 4 hours, and roasting at 450 ℃ for 4 hours to obtain the catalyst, namely 8# catalyst.
Example 9:
13.0g of phosphoric acid (concentration 85 wt%) and 58.6g of molybdenum trioxide (MoO) were weighed out 3 99wt percent of content), 19.6g of basic nickel carbonate (51 wt percent of NiO content) are sequentially added into 100g of deionized water to be heated to boiling, heating is stopped after the solution is clear and transparent, 18.2g of zinc acetate (44 wt percent of ZnO content) is added into the solution after the solution is cooled to room temperature, and the volume of the solution is fixed to 100mL after the solution is completely dissolved, and the solution is marked as 9# solution. The carrier is immersed in the 9# solution by an isovolumetric immersion method, the immersion effect is observed after the carrier is immersed, the immersed carrier is dried for 4 hours at 120 ℃, and the impregnated carrier is roasted for 4 hours at 450 ℃ to obtain the catalyst, which is marked as 9# catalyst.
Example 10:
the impregnation liquid was prepared in the same manner as in example 9, the carrier was impregnated in a 9# solution by an isovolumetric impregnation method, the impregnation effect was observed after the impregnation of the carrier was completed, the completed carrier was dried at 100℃for 5 hours, and the impregnated carrier was calcined at 450℃for 4 hours to prepare a catalyst, designated as a 10# catalyst.
Example 11:
the impregnation liquid was prepared in the same manner as in example 9, the carrier was impregnated in a 9# solution by an isovolumetric impregnation method, the impregnation effect was observed after the impregnation of the carrier was completed, the impregnated carrier was dried at 140℃for 2 hours, and the catalyst was prepared after calcination at 500℃for 3 hours, and designated 11# catalyst.
Example 12:
the impregnation liquid was prepared in the same manner as in example 9, the carrier was impregnated in a 9# solution by an isovolumetric impregnation method, the impregnation effect was observed after the impregnation of the carrier was completed, the impregnated carrier was dried at 140℃for 2 hours, and the catalyst was prepared after calcination at 400℃for 6 hours, and designated as a 12# catalyst.
Example 13:
13.0g of phosphoric acid (concentration 85 wt%) and 58.6g of molybdenum trioxide (MoO) were weighed out 3 99wt percent of content), 13.4g of basic cobalt carbonate (56 wt percent of CoO content) are sequentially added into 100g of deionized water to be heated to boiling, heating is stopped after the solution is clear and transparent, 18.2g of zinc acetate (44 wt percent of ZnO content) is added into the solution after the solution is cooled to room temperature, and the volume of the solution is fixed to 100mL after the solution is completely dissolved, and the solution is marked as 10# solution. The carrier is immersed in the 10# solution by an isovolumetric immersion method, the immersion effect is observed after the carrier is immersed, the immersed carrier is dried for 4 hours at 120 ℃, and the impregnated carrier is roasted for 4 hours at 450 ℃ to obtain the catalyst, which is marked as 13# catalyst.
Comparative example 1:
13.0g of phosphoric acid (concentration 85 wt%) and 58.6g of molybdenum trioxide (MoO) were weighed out 3 15.7g of basic nickel carbonate (NiO content is 51wt%) are added into 100g of deionized water in turn to be heated to boiling, heating is stopped after the solution is clear and transparent, 10g of citric acid is added into the solution after the solution is cooled to room temperature, and the volume is fixed to 100mL after the citric acid is completely dissolved, and the solution is marked as 11# solution. The carrier is immersed in 11# solution by an isovolumetric immersion method, the immersion effect is observed after the carrier is immersed, the immersed carrier is dried for 4 hours at 120 ℃, and the impregnated carrier is roasted for 4 hours at 450 ℃ to obtain the catalyst, which is marked as 14# catalyst.
Comparative example 2:
13.0g of phosphoric acid (concentration 85 wt%) and 58.6g of molybdenum trioxide (MoO) were weighed out 3 15.7g of basic nickel carbonate (NiO content is 51wt%) are added into 100g of deionized water in turn to be heated to boiling, heating is stopped after the solution is clear and transparent, 10g of ethylenediamine tetraacetic acid is added into the solution after the solution is cooled to room temperature, and the volume is fixed to 100mL after the citric acid is completely dissolved, and the solution is marked as 12# solution. The carrier is immersed in a 12# solution by an isovolumetric immersion method, the immersion effect is observed after the carrier is immersed, the immersed carrier is dried for 4 hours at 120 ℃, and the impregnated carrier is roasted for 4 hours at 450 ℃ to obtain the catalyst, which is marked as a 15# catalyst.
Comparative example 3:
6.5g of phosphoric acid (concentration 85 wt%) and 40.4g of molybdenum trioxide (MoO) were weighed out 3 The content of 99 wt%) 14.7g of basic nickel carbonate (NiO content of 51 wt%) is added into 100g of deionized water in turn, heating is stopped after the solution is clear and transparent, 10g of ethylenediamine tetraacetic acid is added into the solution after the solution is cooled to room temperature, and after the ethylenediamine tetraacetic acid is completely dissolved, the volume is fixed to 100mL, and the solution is marked as 13# solution. The carrier is immersed in the No. 13 solution by an isovolumetric immersion method, the immersion effect is observed after the carrier is immersed, the immersed carrier is dried for 4 hours at 120 ℃, and the impregnated carrier is roasted for 4 hours at 450 ℃ to obtain the catalyst, which is marked as No. 16 catalyst.
Example 14:
analysis of MoO in catalysts by EDS Spectrometry 3 The NiO, coO, znO distribution, and the specific results are shown in Table 1.
TABLE 1 impregnating effects of different impregnating solutions
Example 15:
adopting straight-run diesel oil of a certain refinery as a raw material, and passing through a small fixed bed hydrogenation evaluation device at 350 ℃, 6MPa and 2.0h -1 The hydrogenation evaluation is carried out on 14 catalyst samples without hardening phenomenon of the carrier in the catalyst impregnation process under the condition of hydrogen-oil ratio of 400, and the removal effect of the catalyst on sulfides in diesel oil is examined, and the result is shown in Table 2.
TABLE 2 desulfurization Activity of different catalysts
| Catalyst | Desulfurization rate |
| 1# | 93.8 |
| 2# | 95.3 |
| 3# | 96.8 |
| 4# | 96.7 |
| 5# | 95.7 |
| 6# | 97.2 |
| 7# | 96.3 |
| 8# | 95.4 |
| 9# | 99.8 |
| 10# | 99.4 |
| 11# | 98.9 |
| 12# | 99.2 |
| 13# | 98.6 |
| 14# | 92.2 |
From the results of examples and comparative examples, the catalyst preparation method provided by the invention improves the uniformity of the dispersion of the active component molybdenum/nickel in the catalyst and enables the catalyst to exhibit higher hydrodesulfurization activity.
The above examples are exemplary examples listed for the purpose of describing the technical solution of the present invention in detail, the present invention is subject to the protection scope of the claims and the summary of the invention, and is not limited by the embodiments, and the simple substitution or modification of the present invention is still within the protection scope of the present invention.
Claims (9)
1. A method for preparing a diesel hydrodesulfurization catalyst, comprising the steps of:
sequentially adding phosphoric acid, molybdenum oxide and nickel or cobalt salt into deionized water, heating, and cooling after the solution is clear and transparent; adding zinc salt and stirring, and fixing the volume after the zinc salt is completely dissolved to obtain metal impregnation liquid; and (3) immersing the carrier in the metal immersion liquid by adopting an isovolumetric immersion method, and drying and roasting to obtain the diesel hydrodesulfurization catalyst.
2. The method according to claim 1, wherein the heating is performed at a temperature of 60 to 100 ℃ for a time of 0.5 to 2 hours.
3. The method according to claim 1, wherein the temperature is reduced to below 40 ℃.
4. The method according to claim 1, wherein the molybdenum oxide is molybdenum trioxide, the salt of nickel or cobalt is basic carbonate, and the zinc salt is zinc nitrate or zinc acetate.
5. The method according to claim 1, wherein MoO in the metal impregnation liquid is calculated as metal oxide 3 NiO (or CoO), P 2 O 5 The mass ratio of ZnO is 40-60:7.5-15:4-10:4-8.
6. The method according to claim 1, wherein the carrier is composed of alumina and has a clover-shaped outer shape.
7. The method according to claim 1, wherein the drying temperature is 100-140 ℃ and the drying time is 2-5 hours.
8. The method according to claim 1, wherein the firing temperature is 400 to 500 ℃ and the firing time is 3 to 6 hours.
9. A diesel hydrodesulfurization catalyst obtained by the production process according to any one of claims 1 to 8, characterized in that the catalyst comprises MoO in an amount of 100% by mass of the catalyst 3 The content of NiO is 20-28wt%, the content of NiO is 4-6wt%, the content of ZnO is 2-4wt%, and the rest is carrier.
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